Light-sensitive silver halide color photographic emulsion

ABSTRACT

Light-sensitive gelatino-silver halide color photographic emulsions containing a new cyan coupler compound of the formula     X is hydrogen, halogen or an arylazo group. D R A W I N G

United States Patent 1 Sakamoto et al.

[54] LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC EMULSION [75]Inventors: Kenro Sakamoto, Tokyo; Takaya Endo, Hino-shi, Tokyo; MasakuniIwama, Yamato-cho, Tokyo; Isaburo Inoue; Yutaka Takei, both of Hino-shi,Tokyo, all of Japan [73] Assignee: Konishiroku Photo Industry Co., Ltd.,Tokyo, Japan [22] Filed: June 28, 1971 [21] Appl. No; 157,609

Related US. Application Data [63] Continuation of Ser. No 796,927, March5, 1969,

abandoned [52] US. Cl. ..96/100, 96/562, 96/9 [51] Int. Cl. ..G03c 1/40[58] Field of Search ..96/100 [56] References Cited UNITED STATESPATENTS Anderson ..96/ l 00 Anderson ..96/1OO 1 1 Jan. 16, 1973 graphiccmulsions containing a new cyan coupler compound of the formula whereinR is hydrogen or methyl; R is an aliphatic hydrocarbon radical of eightto 20 carbon atoms; n is 1 to 4; m is l or 2; A is a divalent group X ishydrogen, halogen or an arylazo group.

9 Claims, No Drawings LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHICEMULSION This Application isa continuation of our earlier applicationSer. No. 796,927, filed Feb. 5, 1969 and now abandoned.

This invention relates to a light-sensitive gelatinosilver halide colorphotographic emulsion containing a new cyan coupler compound of thegeneral formula wherein R is hydrogen atom or methyl group; R is analiphatic hydrocarbon radical of eight to carbon atoms; n is an integerof l to 4; m is an integer of l or 2; A is a divalent group OH I E H cOHNCHgCHzNHC o onto-Gt 05H This compound has good solubility in highboiling solvents, but it should be synthesized by using, as a startingmaterial, di tert.amyl-phenoxyacetic acid which is very expensive.Another exampleis a coupler of the formula CO(CHz)g-CH which isdisclosed in Japanese Patent Publication No. 2837/1964. This compoundexhibits improved solvent solubility but it should be synthesizedthrough several complicated steps.

We have now found that a compound of the aboveindicated formula is quiteuseful as a protected coupler. This compound can be synthesized bysimple cyclization, with splitting off of water, of a long chain alkylsuccin-monoamide type coupler compound which is conventionally known asso-called Agfa-type coupler,

i.e., an alkali-soluble coupler having ing group.

The coupler compounds of the present invention are readily soluble inhigh boiling solvents such as tricresyl phosphate, dibutyl phthalate,etc. and they are not liable to be separated from coatings after drying.Developed color images obtained with the coupler compounds of theinvention have good spectral absorption characteristics and are stableagainst light, heat and humidity. Remarkable improvements attained bythis invention can be considered due to the existence of a long chainalkyl succinimide group in the molecular structure of new couplercompounds.

The coupler compound of the above-indicated general formula can besynthesized by condensing lhydroxy-2-naphthoic amide derivative having aprimary amino group with a long chain alkyl succinic anhydride inhot'acetic acid. The coupler is dissolved in pyridine and then broughtinto coupling reaction with a diazonium compound, thereby to obtain4-arylazo derivative of high purity. The long chain alkyl succinicanhydride which is the main starting material is prepared in commercialscale by using malonic ester and long chain alkyl halide.

The following are typical couplers useful in this invention. However, itshould be understood that they are not construed as limiting the scopeof the invention.

a diffusion-inhibit- C O-CH2 I c o-cu-omHawtn) 60 OCH;

in the actual use of cyan coupler of this invention, it

CO-CH? propionate, etc. The mixture of the high boiling solvent and lowboiling one also may be used. The resulting solution is mixed with anaqueous gelatine solution,

containing a surface active agent. The resulting mixture is emulsifiedby way of a high speed rotary mixer or a colloid mill. In one way, theresulting emulsion is then directly added to a silver halidephotographic emulsion which in turn is coated on a film base or barytapaper and dried to remove almost all part of the low boiling solvent. inanother way, the above coupler emulsion is once cooled, set, finely cutand washed with water to remove the low boiling solvent, and thereafteris added to a silver halide photographic emulsion which is coated on aphotographic support and dried. The amount of a coupler to be added to aphotographic emulsion may vary within the preferred range of 10 to 100g. per mole of silver halide contained in the emulsion, but this rangeis not critical. Any types of silver halide photographic emulsions canbe used, which include silver chloride, silver iodide, or silverchlorobromide emulsion. Such emulsions may contain sulfur sensitizer,reducing sensitizer, noble metal sensitizer, etc. They can furthercontain any photographic additives conventionally known, e.g.,antifoggant, stabilizer, stain inhibitor, coating aid, etc. Opticalsensitizers for photographic emulsions, e.g., carbocyanine dyes,merocyanine dyes, etc., also can be used. A coupler useful in thisinvention may be incorporated in one or both of the two emulsion layerswhich are coated in superposed relationship and which have colorsensitivity over the same spectral region. Further, the coupler can beused in combination with any conventionally known coupler.

A light-sensitive photographic material obtained by using alight-sensitive color-photographic emulsion of the invention is treated,after imagewise exposure, with a p-phenylenediamine type developersolution and then subjected to bleaching and fixing thereby to give acyan color image having good spectral absorption characteristics withabsorption maximum at 680-690 g.) and good transparency.

The above explanation is given in connection with use ofcolorless-coupler compounds. lf certain arylazo compounds (for example,the compounds (lO)-(l2)) which are orange red or red color are used, thephotographic material containing these when subjected to imagewiseexposure and color development will give a cyan color negative image andan orange-red or red color positive image simultaneously. The positivecolor image serves as a masking image to compensate undesiredabsorptions at the blue and green regions due to the cyan color negativeimage when this cyan color image is to be printed on a positivematerial.

Suitable developers useful for the invention typically include thesulfates, sulfites and hydrochlorides of the following:

N,N-diethyl-p-phenylene diamine,

N-ethyl-N-B-methanesulfonamidoethyl-3-methyl-4- aminoaniline,

N-ethyl-N-hydroxyethyl-p-phenylene diamine,

N-ethyl-N-hydroxyethyl-Z-methyl-p-phenylene diamine, and

N,N-diethyl-Z-methyl-p-phenylene diamine.

Typical synthetic procedures for the couplers will be mentioned below.

Synthesis 1. N-(2-n-octylsuccinimidoethyl)-1- hydroxy-Z-naphthoamide(the compound (1 230 g. of N-(2-aminoethyl)-1-hydroxy-2-naphthoamide and212 g. of n-octylsuccinic anhydride are dissolved in 2 l. of aceticacid. The resulting solution is boiled at reflux for 7 hours and thenadded with 2 l. of methanol. The reaction mixture is allowed to stand atroom temperature and the seperated crystalline mass is collected bysuction filtration, washed with methanol, and dried. Recrystallizationfrom acetonitrile gives 160 g. of white crystalline powder (thecompound 1) The compounds (2) to (8) can be synthesized in the samemanner as of the compound (1).

Synthesis 2.N-[4-(2-n-dodecylsuccinimido-phenoxy)-butyl]-l-hydroxy-Z-naphthoamide(the compound (9) 350 g. ofN-[4-(2-aminophenoxy)-butyl]-1-hydroxynaphthoamide and 268 g. ofn-dodecylsuccinic anhydride are dissolved in 1.5 l. of acetic acid. Theresulting solution is boiled at reflux for 7 hours. The reaction mixtureis poured into 20 l. of water. The separated oily mass is extracted withbenzene and washed with 5 percent aqueous sodium carbonate solution. Thebenzene layer is dehydrated and distilled to remove benzene. The residueis added with n-hexane and the mixture is allowed to remain. Theseparated mass is collected by filtration, washed with n-hexane anddried. 200 g. of pale brown crystalline powder is obtained.

Synthesis 3. N-[3-(n-dodecylsuccinimido)-propyl]-1-hydroxy-4-(2-ethoxycarbonyl-phenylazo)-(the compound (10) 165.2 g. ofethyl anthranilate dissolved in dilute hydrochloric acid is added withan aqueous sodium nitrite solution. The diazotized solution is added atroom temperature to 490 g. of N-[S-(n-dodecyl-succinimido )-propyl]- l-hydroxy-2-naphthoamide dissolved in 4 1. of pyridine, with stirring.Stirring is continued for 30 minutes at room temperature. To themixture, 5 l. of acetonitrile is added. The separated crystalline massis collected by filtration, washed with acetonitrile and dried.Recrystallization from n-hexane and ethyl acetate (1:1) gives 580 g. ofred crystalline powder (the compound (10) The compounds (11) to (13) canbe synthesized in the same manner as above.

The melting points and elementary analyses of the thus obtained couplersare listed in Table 1.

EXAMPLE 1 20 g. of the coupler compound (2) is dissolved at 80C in amixture of 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate. Theresulting solution is mixed with 10 ml. of an aqueous solution of 10percent Alkanol B (alkyl naphthalene sulfonate produced by Du Pont,U.S.A.) and 200 ml. of an aqueous 5 percent gelatine solution. Theresulting mixture is treated in a colloid mill. The thus obtainedcoupler dispersion is added to 1 kg. of a high speed gelatino-silveriodobromide photographic emulsion, which is then coated on a film baseand dried.

The light-sensitive photographic film obtained is exposed to light andthen treated at 20C for 10 minutes with a developing solution of thefollowing formulation:

N,N-diethyl-p-phenylenediamine 2.5 g. hydrochloride Anhydrous sodiumsulfite 2.0 g. Sodium carbonate monohydrate 82.0 g. Potassium bromide2.0 g.

Water to make up 1 l.

The developed film is treated in the ordinary manner by stopping andfixing and then, after washing with water for 10-15 minutes, treated for5 minutes with a bleaching bath of the following formulation:

Potassium ferricyanide Potassium bromide Water to make up 1 l.

I00 g. g.

The film is washed with water for 5 minutes and further treated for 5minutes in a fixing bath of the following formulation:

Sodium thiosulfate pentahydrate Water to make up 1000 ml.

The film is washed with water for 20-25 minutes and dried. Clear cyancolor image having absorption maximum at 690 p. is obtained.

EXAMPLE 2 TABLE 1 Elementary analysis (percent) Calcd. Found Solvent forrecrystallization C H N C H N Acetonitrlle 70. 72 7. 6. 60 70. 50 7. 426. 38 n-Hexane. 72.84 8. 56 5. 66 72.55 8.61 5. 71 0 68.67 8.00 5.3067.79 7.98 5.48 Ethanol... 74. 9. 40 4.84 74. 81 9. 77 5. 11 .do 77.088.52 4.39 76.10 8.91 4. 40 Methanol plus acetic acid. 73.13 7.93 4. 1672. 87 8.35 4.40 Ethyl acetal 76. 64 8. 68 4. 47 76. 36 8.92 4. 54....do 75.19 8.71 4.18 75.37 9.06 4.34 n-Hexane 73.97 8.05 4. 66 73.938. 50 4. 92 n-Hexane plus ethyl acetate..- 69. 82 7. 51 8. 35 70.12 7.8. 52 Ethanol plus n-Hexane 71. 22 7. 55 8. 75 71.04 7. 71 8. 99Methanol 74. 38 8.06 7. 23 74. 26 8. 31 7. 42 Ethyl acetate 73. 50 7.6.86 73.21 8. 21 6. 75

The following examples will explain the invention in detail, withoutlimiting its scope thereto.

film base and dried.

The photographic film thus obtained is exposed to light and treated at20C for 10 minutes with a developing solution of the formulation:

Metol Anhydrous sodium sulfite 603) 8- Hydroquinone 6.0 g. Anhydroussodium carbonate 8- Potassium bromide 2- Water to make up 1000 ml.

After following ordinary stopping, film hardening and water-washingsteps, the film is subjected to secondary exposure using white light andthen treated at 20C for 12 minutes with a developing solution of theformulation:

N,N-diethyl-p-phenylenediamine 5.0 g. hydrochloride Anhydrous sodiumsulfite 2.0 g. Sodium carbonate (monohydi'ate) 82.0 g. Potzmsium bromide1.0 g.

Water to make up 1000 ml.

The film is followed by ordinary stopping, fixing, water' washing andbleaching steps. After washing for 20 minutes with running water anddrying, clear cyan color positive image having absorption maximum at 685p. is obtained.

EXAMPLE 3 10.0 g. of the coupler compound (6) is dissolved at 50C in 20ml of dibutyl phthalate. The resulting solution is mixed with ml of anaqueous solution of 10 percent Alkanol B and 200 ml of an aqueous 5percent 'gelatine solution. The resulting mixture is passed through acolloid mill several times to form a dispersion. The resultingdispersion is added to 500 g of a gelatino-silver chlorobromideemulsion, which is then coated on a baryta paper and dried.

The light-sensitive photographic material thus formed is exposed tolight and then treated at C for 10 minutes with a developing solution ofthe following formulation:

N ethyl-N-hydroxyethyl-p-phenylene- 2.5 g. diamine sulfate Anhydroussodium sulfite 2.0 g. l-lydroxyamine hydrochloride 1.0 g. Sodiumcarbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g.

Water to make up i000 ml.

Ethylenediaminetetraacetic acid 40.0 g. disodium salt Ferric chloride30.0 g. Sodium carbonate (monohydrat'e) 20.0 g. Potassium bromide 30.0g. Sodium thiosulfate (pentahydrate) 200.0 g.

Water to make up 1000 ml The material is washed with water for 20minutes and then treated for 2 minutes in a stabilizing bath and dried.A cyan color image having absorption maximum at 695 p. and excellent infastness to light and heat as well as in storability is obtained.

8 EXAMPLE 4 2.0 g. of the coupler compound (10) is dissolved in themixture of 2 ml of dibutyl phthalate and 6 ml of butyl acetate at C. Theresulting solution is mixed with 1 ml of an aqueous solution of 10percent Alkanol B and 20 ml of an aqueous 5 percent gelatine solution toform a dispersion.

The coupler dispersion thus obtained is added to g of a high speedgelatino-silver bromoiodide emulsion, which is then coated on a filmbase and dried.

The light-sensitive photographic material thus obtained is then exposedto light and treated with the developing solution as usedin theExample 1. A red positive image having absorption maximum of 500 p. anda cyan color image having absorption maximum at 690 p. are obtained.

EXAMPLE 5 2.0 g of the coupler compound (2) is dissolved in 5 ml ofbutyl acetate and the resulting solution is mixed with 1.5 ml of anaqueous solution of 10 percent A1- kanol and 20 ml of an aqueous 5percent gelatine solution to form a dispersion.

The coupler dispersion thus obtained is added to 100 g of a redsensitive high speed gelatino-silver iodobromide emulsion, which is thencoated on a film base and dried.

After exposure to light in the ordinary manner, the film is treated withthe developing solution as used in the Example IV A clear cyan colorimage having absorption maximum of 685 u is obtained.

We claim:

1. A light-sensitive silver halide color photographic emulsion havingdispersed therein a solution of a cyan coupler in a high boilingsolvent, said cyan coupler having the general formula wherein R ishydrogen or a methyl group, R is an aliphatic hydrocarbon radical ofeight to 20 carbon atoms, n is an integer of l 4, m is l or 2, A is adivalent group of 2 or -0- E); and

x is hydrogen, a halogen, anaryl azo group or an aryl azo groupsubstituted by a lower alkoxycarbonyl, lower acyl, lower alkyl or loweralkoxygroup.

2. A light-sensitive silver halide color photographic emulsion asclaimed in claim 1, wherein said cyan coupler is a compound of thefollowing structural formula 3. A light-sensitive silver halide colorphotographic emulsion as claimed in claim 1, wherein said cyan coupleris a compound of the following structural formula C O-GH:

4. A light-sensitive silver halide color photographic emulsion asclaimed in claim 1, wherein said cyan coupler is a compound of thefollowing structural formula 5. A light-sensitive silver halide colorphotographic emulsion as claimed in claim 1, wherein said cyan coupleris a compound of the following structural formula 6. A light-sensitivesilver halide color photographic emulsion as claimed in claim 1, whereinsaid cyan coupler is a compound of the following structural formula COHN-CHr-CHr-CHz-O CO-OHQ 7. A light-sensitive silver halide colorphotographic emulsion as claimed in claim 1, wherein said cyan coupleris a compound of the following structural formula (JO-CH2 I N=N (5O OC Hl N=N O C Ha 9. A light-sensitive silver halide color photographicemulsion as claimed in claim 1, wherein said cyan coupler is a compoundof the following structural formula OCHa

2. A light-sensitive silver halide color photographic emulsion asclaimed in claim 1, wherein said cyan coupler is a compound of thefollowing structural formula
 3. A light-sensitive silver halide colorphotographic emulsion as claimed in claim 1, wherein said cyan coupleris a compound of the following structural formula
 4. A light-sensitivesilver halide color photographic emulsion as claimed in claim 1, whereinsaid cyan coupler is a compound of the following structural formula
 5. Alight-sensitive silver halide color photographic emulsion as claimed inclaim 1, wherein said cyan coupler is a compound of the followingstructural formula
 6. A light-sensitive silver halide color photographicemulsion as claimed in claim 1, wherein said cyan coupler is a compoundof the following structural formula
 7. A light-sensitive silver halidecolor photographic emulsion as claimed in claim 1, wherein said cyancoupler is a compound of the following structural formula
 8. Alight-sensitive silver halide color photographic emulsion as claimed inclaim 1, wherein said cyan coupler is a compound of the followingstructural formula
 9. A light-sensitive silver halide color photographicemulsion as claimed in claim 1, wherein said cyan coupler is a compoundof the following structural formula